[noun] + の中で [noun] + の中で + [noun] + が + 一番 / 最も + [i-adj] [noun] + の中で + [noun] + が + 一番 / 最も + [na-adj] [noun] + の中で + [question word] + が + 一番 + [i-adj]
の中で follows a noun and means "among" or "inside". Most often it names the group a superlative is drawn from, with いちばん一番 or the more formal もっとも最も, and the one picked out takes が.
The superlative with question words has its own entry, ~の中で~が一番.
Taken literally, の中で is "inside", and で marks the place as where something is done. The place can also be a group or an organisation.
で marks where something is done. に marks where something is, or where it goes, so ある, いる and はいる入る take の中に.